CN101679152A - Method of preparing iodinated aromatic compounds - Google Patents
Method of preparing iodinated aromatic compounds Download PDFInfo
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- CN101679152A CN101679152A CN200880016638A CN200880016638A CN101679152A CN 101679152 A CN101679152 A CN 101679152A CN 200880016638 A CN200880016638 A CN 200880016638A CN 200880016638 A CN200880016638 A CN 200880016638A CN 101679152 A CN101679152 A CN 101679152A
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- Prior art keywords
- aromatic compound
- iodo aromatic
- iodo
- aromatics
- iodine
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- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000006192 iodination reaction Methods 0.000 claims abstract description 56
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 50
- 239000011630 iodine Substances 0.000 claims abstract description 46
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 34
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000010457 zeolite Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 90
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims description 23
- 238000004821 distillation Methods 0.000 claims description 22
- KFZGFJXYQHKJJV-UHFFFAOYSA-N benzene dihydroiodide Chemical compound I.I.C1=CC=CC=C1 KFZGFJXYQHKJJV-UHFFFAOYSA-N 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 16
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 238000011084 recovery Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 239000012452 mother liquor Substances 0.000 claims description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 239000004305 biphenyl Substances 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- -1 iodate biphenyl Chemical group 0.000 claims description 3
- FILHQJVXWYVHJK-UHFFFAOYSA-N iodic acid naphthalene Chemical class I(=O)(=O)O.C1=CC=CC2=CC=CC=C12 FILHQJVXWYVHJK-UHFFFAOYSA-N 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 abstract description 19
- 238000002360 preparation method Methods 0.000 abstract description 14
- 230000002083 iodinating effect Effects 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 4
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 230000026045 iodination Effects 0.000 abstract 1
- 230000001629 suppression Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 230000009466 transformation Effects 0.000 description 9
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000374 eutectic mixture Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000007616 round robin method Methods 0.000 description 2
- WRTMQOHKMFDUKX-UHFFFAOYSA-N triiodide Chemical compound I[I-]I WRTMQOHKMFDUKX-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KOQIGXPORFDMML-UHFFFAOYSA-N benzene trihydroiodide Chemical compound C1=CC=CC=C1.I.I.I KOQIGXPORFDMML-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-N iodic acid Chemical class OI(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/392—Separation; Purification; Stabilisation; Use of additives by crystallisation; Purification or separation of the crystals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a method of preparing iodinated aromatic compounds, and more preferably a method of preparing iodinated aromatic compounds comprising a step of iodinating a react antincluding an aromatic compound, a di-iodo aromatic compound or water, and iodine (I2) in the presence of a zeolite catalyst and oxygen. The method of the present invention has an advantage that by iodination of a reactant including the aromatic compound, and the di-iodo aromatic compound or water in the presence of the zeolite catalyst and oxygen, the temperature of the iodinating reactor can be controlled reliably and constantly, thereby resulting in improved productivity per unit weight of catalyst and inhibition of a side reaction in accordance with suppression of producing impurities. In addition, the productivity of the iodinated aromatic compound, preferably the di-iodo aromatic compound, more preferably a p-di-iodo aromatic compound can be improved, and thus can be widely used in the preparation of a di-iodo aromatic compound such as a p-di-iodo aromatic compound.
Description
Technical field
The present invention relates to a kind of method for preparing iodinated aromatic compounds, relate more specifically to a kind of method for preparing iodinated aromatic compounds that comprises the steps: in the presence of zeolite catalyst and oxygen, make to comprise a kind of aromatics, a kind of di-iodo aromatic compound or water and iodine (I
2) the mixture iodate.
Background technology
The method that the reactant that use comprises a kind of aromatics such as benzene or naphthalene and a kind of halogen (bromine, chlorine, iodine etc.) prepares halogenated aromatic compounds receives publicity in industrial circle always.Particularly, in above-mentioned halogenated aromatic compounds, paradiiodobenzene (p-DIB) is widely used as producing the reactant of polyphenylene sulfide (PPS), and its commercial value is very high, and is therefore very active always to the research that improves p-DIB productivity.
For example, as shown in Figure 1, US 4,778,938 and US 4,746,758 a kind of benzene and iodine (I of using in the presence of zeolite catalyst and oxygen disclosed
2) prepare the method for p-DIB as reactant.According to these prior aries, has advantage aspect the transformation efficiency of these preparation methods in p-DIB produces.In addition, according to the disclosure of above-mentioned prior art, these methods also can minimize the oxidizing reaction of benzene or naphthalene.
Yet there is shortcoming in aforesaid method aspect the temperature of control iodination reaction device, and described temperature is relevant with the local a large amount of thermopositive reaction that take place.As a universal law, in the presence of zeolite catalyst and oxygen, the iodate of aromatics must be accompanied by hydrogen iodide (hydroiodic acid HI, oxidation HI).The oxidation of this HI is a kind of reaction of a large amount of heat releases, and has therefore improved the temperature at described iodination reaction device center.Under this hot conditions, the iodate of reactant and combustion reactions are all very violent, and therefore cause a large amount of uncontrolled reactions.In addition, when these preparation methods were used for plant size and design described factory, temperature control became more important and is top-priority, because the diameter of described reactor should be designed to be enough big.
In addition, under this hot conditions, the combustion reactions meeting of described reactant causes the formation of impurity such as carbon deposits, thereby makes described catalyst deactivation also therefore shorten the replacement cycle of described catalyzer.In addition, owing to be difficult to control the temperature of described iodination reaction device, therefore can not increase the feed rate of described reactant, thereby productivity descends.
Summary of the invention
For solving the problem of above-mentioned ordinary method, the invention provides a kind of method for preparing iodinated aromatic compounds, described method can reliablely and stablely be controlled the temperature of iodination reaction device, thereby improves the productivity of per unit weight catalyzer and the side reaction that inhibition forms impurity.
One embodiment of the invention relate to a kind of method for preparing iodinated aromatic compounds, comprising:
In the presence of zeolite catalyst and oxygen, make and comprise a kind of aromatics, a kind of di-iodo aromatic compound or water and iodine (I
2) the mixture iodate.
Described aromatics can be selected from benzene, naphthalene and biphenyl.
In addition, described di-iodo aromatic compound can be selected from benzene diiodide, two iodate naphthalenes and two iodate biphenyl.
For reliablely and stablely controlling the temperature of iodination reaction device, described two iodate aromatic series chemical combination and water can use with the mol ratio that is respectively 2-10 mole % and 5-30 mole % with respect to described aromatics.
In addition, described zeolite catalyst can be selected from Na-13X zeolite, y-type zeolite, ZSM5 zeolite and K-13X zeolite.
More preferably, described zeolite catalyst can be the Na-13X zeolite.
In addition, described iodination reaction can be carried out under 230-350 ℃ and normal pressure to 5 normal atmosphere.
Method of the present invention also can comprise:
Make the di-iodo aromatic compound circulation that comprises di-iodo aromatic compound, adjacent di-iodo aromatic compound and a di-iodo aromatic compound,
Wherein said di-iodo aromatic compound obtains in the following manner:
Distillation is by comprising described aromatics, described di-iodo aromatic compound or water and iodine (I
2) the iodate product that obtains of mixture, and overhead product carried out crystallization and solid-liquid separation.
The method that the present invention prepares iodinated aromatic compounds also can comprise:
To be delivered to first distillation tower (C10) from iodination reaction device (R01) by the iodate product that the mixture that comprises described aromatics, described di-iodo aromatic compound or water and iodine obtains, then described aromatics of Separation and Recovery and water from the iodate product at first distillation tower (C10) top;
The overhead product of first distillation tower (C10) bottom is delivered to second column (C20), then Separation and Recovery monoiod(in)ate aromatics and iodine from the overhead product at second column (C20) top;
The overhead product of second column (C20) bottom is delivered to the 3rd distillation tower (C30), Separation and Recovery and is delivered to them in crystallization and the solid-liquid separator (D10) di-iodo aromatic compound, adjacent di-iodo aromatic compound and a di-iodo aromatic compound from the overhead product at the 3rd distillation tower (C30) top then;
The Separation and Recovery solid phase is to di-iodo aromatic compound with comprise the mother liquor of liquid phase to di-iodo aromatic compound, adjacent di-iodo aromatic compound and a di-iodo aromatic compound from crystallization and solid-liquid separator (D10); With
By making described di-iodo aromatic compound circulation in the part input iodination reaction device (R01) with described mother liquor.
Description of drawings
For the present invention and advantage thereof there being one understand more completely, this paper has done following explanation in conjunction with the accompanying drawings with as a reference, in the accompanying drawing:
Fig. 1 is the synoptic diagram that shows according to the iodinated aromatic compounds preparation method of Comparative Examples 1 and 2;
Fig. 2 is the synoptic diagram that shows according to the iodinated aromatic compounds preparation method of embodiment 1 and 2;
Fig. 3 shows according to one embodiment of the invention, and the preparation iodinated aromatic compounds also makes a kind of synoptic diagram of di-iodo aromatic compound round-robin method of low solutrope form; With
Fig. 4 is the detail drawing of described iodination reaction device (R01).
Reference numeral describes in detail
R01: iodination reaction device C10: first distillation tower
C20: second column C30: the 3rd distillation tower
D10: crystallization and solid-liquid separator
Embodiment
Above-mentioned purpose of the present invention and other purposes can be from following to being better understood explanation of the present invention, Figure of description and the claims.
Yet the present invention is not limited to following examples, but numerous embodiments is arranged, and these embodiment are provided, and just present invention is described, and the present invention only limits by claims.
Below the present invention is described in detail.
Method of the present invention has the following advantages: comprise a kind of aromatics, a kind of di-iodo aromatic compound or water and iodine (I by making in the presence of zeolite catalyst and oxygen
2) the mixture iodate, can reliablely and stablely control the temperature of iodination reaction device, thereby improve the productivity of per unit weight catalyzer iodinated aromatic compounds and suppress to form the side reaction of impurity.
In addition, owing to also comprise multistep distillation, crystallization and solid-liquid separation in embodiment of the present invention, therefore can circulate by the di-iodo aromatic compound that the inventive method obtains.
" aromatics " of the present invention is defined as non-halogenated aromatics such as benzene, naphthalene and biphenyl, " monoiod(in)ate aromatics " or " monoiod(in)ate compound " is defined as an aromatics that hydrogen atom is replaced by the iodine atom of aromatics, as monoiod(in)ate benzene.
In addition, " di-iodo aromatic compound " or " two iodate compounds " is defined as the aromatics that any two hydrogen atoms of aromatics are replaced by the iodine atom, as benzene diiodide.In addition, di-iodo aromatic compound has three kinds of isomer, promptly to di-iodo aromatic compound, adjacent di-iodo aromatic compound and a di-iodo aromatic compound.In addition, the above hydrogen atom that " iodinated aromatic compounds " of the present invention's preparation is defined as aromatics is comprised monoiod(in)ate aromatics, di-iodo aromatic compound and triiodide aromatics by the aromatics that the iodine atom replaces.
In addition, " iodate " of the present invention be defined as aromatics such as benzene and naphthalene and iodine (I
2) reaction, be substituted by the iodine atom with hydrogen atom with described aromatics.By iodate, can obtain monoiod(in)ate aromatics and many iodinated aromatic compounds, as di-iodo aromatic compound and triiodide aromatics.
Consult Fig. 2, preparation method of the present invention has the following advantages: comprise a kind of aromatics, a kind of di-iodo aromatic compound or water and iodine (I by making in the presence of zeolite catalyst and oxygen
2) the mixture iodate, can reliablely and stablely control the temperature of iodination reaction device, thereby improve the productivity of iodinated aromatic compounds.
One embodiment of the invention relate to a kind of preparation method of iodinated aromatic compounds, comprising:
In the presence of zeolite catalyst and oxygen, make and comprise a kind of aromatics, a kind of di-iodo aromatic compound or water and iodine (I
2) the mixture iodate.
That is to say that according to above-mentioned embodiment of the present invention, it is use iodine (I by a kind of di-iodo aromatic compound being added a kind of aromatics----
2) iodinating object----can suppress the side reaction that caused by iodinated aromatic compounds such as monoiod(in)ate aromatics and di-iodo aromatic compound, thereby can reliablely and stablely control the temperature of described iodination reaction device.In addition, by suppressing the iodinated aromatic compounds side reaction of monoiod(in)ate aromatics and described di-iodo aromatic compound as described, the productivity of described iodinated aromatic compounds (especially di-iodo aromatic compound) and all can be increased significantly to the very high selectivity of commercial value to di-iodo aromatic compound.
Above-mentioned embodiment embodiment according to the present invention, it is use iodine (I by water being joined a kind of aromatics----
2) can control the oxidizing reaction (very exothermic reaction) of hydrogen iodide in the iodinating object----reliably, and therefore can reliablely and stablely control the temperature of iodination reaction device.
Therefore, by arbitrary embodiment according to the present invention with described di-iodo aromatic compound or water join aromatics----its for iodine (I
2) can remain on very high level with the productivity of described di-iodo aromatic compound with to the selectivity of di-iodo aromatic compound in the iodinating object----.In addition, can reliablely and stablely control the temperature of described iodination reaction device, therefore can increase the feed rate of described reactant, thereby can increase the very high productivity of described commercial value di-iodo aromatic compound.
As a universal law, in the presence of zeolite catalyst, the iodate of aromatics is accompanied by the absorption and the desorption of reactant and product.Particularly, reactant is attracted on the zeolite catalyst, then after iodate with the form of iodinated aromatic compounds by desorption.On average, described absorption/desorption is more violent on the top of described iodination reaction device.Therefore, the heat of reaction part emits, so the local temperature of reactor is higher.Yet according to the present invention, described absorption/desorption carries out in whole reactor equably, and the side reaction that therefore can reliablely and stablely control the temperature of iodination reaction device and suppress to cause owing to the temperature raising.
In addition, the present invention can make the generation of carbonic acid gas and carbon deposits minimize, thereby can prolong the cycle that zeolite catalyst is changed.In addition, the present invention can improve the productivity of the very high iodinated aromatic compounds of commercial value.
In the iodate of above-mentioned embodiment of the present invention, the existence of oxygen is essential.The hydrogen iodide that forms in iodination reaction should be oxidized to iodine (I
2) to participate in iodination reaction again.Therefore, when not having oxygen or only there is minor amounts of oxygen in hydrogen iodide relatively, the water that produces in hydrogen iodide and the oxidizing reaction constitutes conventional ratio, and described treating process is had harmful effect, and may pass through intensive oxidizing reaction etching apparatus.
Back pressure regulator control iodination reaction pressure shown in Figure 2 also makes and can carry out compressive reaction.Sample disposal system shown in Figure 2 is removed the steam that is included in the gas with the shielding gas analyser.In addition, described gas analyzer can be used for concentration of carbon dioxide in the analytical gas.
Zeolite catalyst of the present invention can be selected from y-type zeolite, ZSM5 zeolite and K-13X zeolite, but is not limited to these, preferably can be the Na-13X zeolite.
In addition, aromatics of the present invention preferably can be selected from benzene, naphthalene and biphenyl, and di-iodo aromatic compound of the present invention preferably can be selected from benzene diiodide, two iodate naphthalenes and two iodate biphenyl.
Described aromatics and iodine (I
2) mol ratio can change according to reaction conditions.If use a large amount of iodine (I
2), then as iodine (I
2) transformation efficiency when low the productivity of many iodinated aromatic compounds increase.Yet, if for increasing iodine (I
2) transformation efficiency and use with respect to iodine (I
2) a large amount of aromatics, then can increase iodine (I
2) transformation efficiency, but can reduce the productivity of described di-iodo aromatic compound.Therefore, consider the purpose of described iodization, can be to described aromatics and iodine (I
2) mol ratio suitably control, preferably use with the mol ratio (aromatics/iodine) of 0.3-3.0.
In addition, described di-iodo aromatic compound can be used according to the mol ratio that with respect to described aromatics is 2-10 mole %, and water can be according to being that the mol ratio of 5-30 mole % is used to described aromatics relatively.
In addition, water can be tap water or distilled water, but is not limited to these.
The temperature curve of iodination reaction according to an embodiment of the invention, regulate described temperature of reaction high more, the transformation efficiency of described reactant (aromatics and iodine) is high more, and the very high selectivity to di-iodo aromatic compound of described commercial value is low more.In addition, can in various pressure ranges, regulate the pressure of described reaction.Regulate the pressure of described reaction higher, can improve the efficient of iodination reaction.By last, described iodination reaction preferably can be carried out under 230-350 ℃ and normal pressure to 5 normal atmosphere.
In addition, described di-iodo aromatic compound can obtain according to general preparation method or by commercial the purchase, but is not limited thereto.And, its can be preferably according to the present invention another also comprise a plurality of steps as the embodiment of distillation, recrystallization and solid-liquid separation be by reactant as described in aromatics, as described in di-iodo aromatic compound or water and iodine (I
2) the reaction product of iodination reaction obtain.In addition, described di-iodo aromatic compound comprises three kinds of isomer, promptly to di-iodo aromatic compound, adjacent di-iodo aromatic compound and a di-iodo aromatic compound.
Consult Fig. 3, preparation method's preferred implementation also comprises a kind of described di-iodo aromatic compound round-robin method that makes, and described circulation means can comprise:
Will be by comprising described aromatics, described di-iodo aromatic compound or water and iodine (I
2) the iodate product that obtains of mixture be transported to first distillation tower (C10) from iodination reaction device (R01), described aromatics of Separation and Recovery and water from the iodate product at first distillation tower (C10) top then;
The overhead product of first distillation tower (C10) bottom is delivered to second column (C20), then Separation and Recovery monoiod(in)ate aromatics and iodine (I from the overhead product at second column (C20) top
2);
The overhead product of second column (C20) bottom is delivered to the 3rd distillation tower (C30), Separation and Recovery comprises di-iodo aromatic compound to di-iodo aromatic compound, adjacent di-iodo aromatic compound and a di-iodo aromatic compound from the overhead product at the 3rd distillation tower (C30) top then, and they are delivered in crystallization and the solid-liquid separator (D10);
The Separation and Recovery solid phase is to di-iodo aromatic compound with comprise the mother liquor of liquid phase to di-iodo aromatic compound, adjacent di-iodo aromatic compound and a di-iodo aromatic compound from crystallization and solid-liquid separator (D10); With
By making described di-iodo aromatic compound circulation in the part input iodination reaction device (R01) with described mother liquor.
Described fusing point to benzene diiodide, a benzene diiodide and adjacent benzene diiodide is respectively 131 ℃, 36 ℃ and 27 ℃.Therefore, according to one embodiment of present invention, the benzene diiodide that obtains from the 3rd distillation tower (C30) top exists in the form of normal temperature (25 ℃) with liquid and solid mixture (eutectic mixture).Particularly, recrystallization with separate after, the mother liquor that comprises 15.4% pair of benzene diiodide, 71.5% benzene diiodide and 15.4% adjacent benzene diiodide can solid-stately separate benzene diiodide with pure.Can find out thus, (to,, the neighbour) three kinds of isomer form a kind of eutectic mixture, thereby can exist with liquid form at normal temperatures under the temperature that is lower than described three kinds of isomer fusing points.By making the benzene diiodide in the above-mentioned mother liquor loop back iodination reaction device (R01), can solve one object of the present invention.
In addition, Fig. 4 is the detail drawing of the iodination reaction device (R01) shown in Fig. 2 and Fig. 3.Fig. 4 has shown the catalyst bed that iodination reaction device (R01) is inner particularly, and a thermocouple movably.Zeolite catalyst is loaded in the inside of iodination reaction device (R01), and is supported and the oil jacket encirclement by catalyst bed.In addition, one movably thermocouple be loaded into the inside of described catalyst bed, as shown in Figure 4.Constant for keeping temperature of reaction, can be from the bottom fuel feeding of oil jacket, oil absorbs the high calorie in the described iodination reaction, reclaims from the top of oil jacket after making its top that is circulated to oil jacket.As mentioned above, by circulating and refiltered oil with described oil jacket, the temperature of described iodination reaction device can be stabilized control reliably.
With reference to following examples the present invention is further elaborated.Yet these embodiment should not be interpreted as limiting the scope of the invention in any form.
Provided below and to be used term among the Comparative Examples of proof practicality of the present invention and the embodiment.
At first, the ratio of " aromatic series/I " has been described the mol ratio of used aromatics and iodine.Particularly, be the preparation benzene diiodide, benzene should with 1 mole of iodine (two iodine atoms, I
2) reaction.Therefore, aromatic series/I such as following formula 1 definition.
[formula 1]
Mole number * 2 of aromatic series/I=[(benzene)+(mole number of monoiod(in)ate benzene)]/iodine (I
2) * 2
In addition, be used to prove that the term of described reaction product and method practicality is as follows.At first, the productivity of p-DIB is defined as the turnout of the p-DIB of time per unit and per volume of catalyst.Its unit expresses with g/lh.Iodine (I
2) and the transformation efficiency of benzene be defined as the iodine (I of conversion
2) or the amount and the iodine (I of benzene
2) or the ratio of the amount of benzene, this ratio is represented with per-cent (%).
The iodinating benzene that is produced by described iodination reaction comprises monoiod(in)ate benzene (MIB), benzene diiodide (DIB) and triiodide benzene (TIB), and DIB and TIB have three kinds of isomer respectively.Particularly, DIB comprises benzene diiodide (p-DIB), adjacent benzene diiodide (o-DIB) and three kinds of isomer of a benzene diiodide (m-DIB).In addition, " total DIB " can be defined as the p-DIB, the o-DIB that are produced and the m-DIB total weight percent with respect to product, shown in following formula 2.
[formula 2]
Total DIB=(p-DIB+m-DIB+o-DIB)/(product) * 100
In addition, selectivity can be defined as p-DIB with respect to the weight percent of three kinds of DIB that produced, shown in following formula 3.
[formula 3]
Selectivity=(p-DIB)/(p-DIB+m-DIB+o-DIB) * 100
According to the present invention, can effectively make commercial value very high to di-iodo aromatic compound, this can be drawn by high " total DIB " and " selectivity of p-DIB ".
Comparative Examples 1
Use iodination reaction device shown in Figure 1, do not add DIB, have only benzene (176.4g/h), iodine (I
2) (275.0g/h) react with air.Iodine (I
2) and air by preheater and be heated to 200 ℃, be conducted to iodination reaction device (R01) then.In addition, benzene also is heated to 200 ℃ and use other feeding lines to supply with the form of steam.The temperature of reaction of iodination reaction device is controlled by the temperature that control supplies to the oil of oil jacket.The temperature regulation of the iodination reaction device that will measure at the inside center place of iodination reaction device is constant for 280 ℃ of maintenances.But temperature of reaction is not to remain unchanged.The temperature on the top of iodination reaction device is higher than ideal temperature.And the temperature of iodination reaction device descends along the flow direction of reactant.Be to check the temperature curve of iodination reaction device, temperature measuring equipment such as thermocouple sleeve pipe and thermocouple are installed in the inside center of iodination reaction device.Regularly detect the temperature of upper, middle and lower of iodination reaction device to determine highest temperature region with the removable thermocouple that can be in the iodination reaction device moves up and down then.After reaching reaction conditions, make to be reflected at normal temperature and to carry out 24 hours.Then, after iodate, carry out sampling and analysing, described reaction conditions and the results are shown in the following table 1.
Comparative Examples 2
Except benzene and iodine (I
2) supply be respectively beyond 265.2g/h and the 412.5g/h, it is identical with Comparative Examples 1 that all reaction conditionss all are adjusted to.In Comparative Examples 2, can not carry out reliable and stable control to temperature of reaction.That is, the upper temp of iodination reaction device is elevated to more than 380 ℃, therefore described reaction terminating.When temperature of reaction was higher than said temperature, a large amount of uncontrolled reactions can take place in benzene, caused a large amount of depositions of carbon compound then.
Use is shown in the iodination reaction device of Fig. 2, except with benzene (565.2g/h), benzene diiodide (83.4g/h) and iodine (I
2) (900.1g/h) be supplied to beyond the iodination reaction device, it is identical with Comparative Examples 1 that all reaction conditionss all are adjusted to.Reaction conditions and reaction result are shown in the following table 1.Used DIB from three kinds of isomer (to, adjacent and) mother liquor obtain, described mother liquor is to separate acquisition with pure p-DIB crystalline solid.
Embodiment 2
Except benzene, water and iodine (I
2) supply be respectively beyond 550.0g/h, 35g/h and the 744.1g/h, it is identical with Comparative Examples 1 that all reaction conditionss all are adjusted to.Reaction conditions and reaction result are shown in the following table 1.
[table 1]
| Comparative Examples 1 | Comparative Examples 2 | |
Embodiment 2 | ||
| Benzene | ??g/h | ??176.4 | ??265.2 | ??565.2 | ??550.0 |
| Iodine | ??g/h | ??275.0 | ??412.5 | ??900.1 | ??744.1 |
| Aromatic series/I | Mol ratio | ??2.08 | ??2.09 | ??2.04 | ??2.40 |
| ??DIB | ??g/h | ??0 | ??0 | ??83.4 | ??0 |
| Water (H 2O) | ??g/h | ??0 | ??0 | ??0 | ??35 |
| Benzene | Weight % | ??14.96 | ??12.56 | ??16.71 | |
| ??MIB | Weight % | ??50.40 | ??40.99 | ??45.31 | |
| ??p-DIB | Weight % | ??22.33 | ??30.69 | ??22.06 | |
| ??m-DIB | Weight % | ??5.76 | ??4.88 | ??5.59 | |
| ??o-DIB | Weight % | ??1.12 | ??1.45 | ??1.86 | |
| ??TIB | Weight % | ??1.72 | ??2.13 | ??3.22 | |
| The productivity of p-DIB | ??g/l·h | ??13.80 | ??64.24 | ??40.74 | |
| ??I 2Transformation efficiency | ??％ | ??97.64 | ??94.84 | ??97.81 | |
| The transformation efficiency of benzene | ??％ | ??63.33 | ??67.44 | ??60.64 | |
| Total DIB | Weight % | ??30.33 | ??39.93 | ??31.14 | |
| The selectivity of p-DIB | ??％ | ??76.45 | ??82.90 | ??74.75 | |
| Carbon deposits | ??g/kg | ??0.78 | ??0.64 | ??0.59 | |
| ??CO 2 | ??％ | ??2.33 | ??1.07 | ??0.98 |
As shown in table 1, the selectivity of total DIB, p-DIB and the transformation efficiency of reactant almost do not have difference between described Comparative Examples and embodiment.As mentioned above, as removing iodine (I
2) in addition reactant, 1 of Comparative Examples has been used benzene, and embodiment 1 has used benzene and DIB, and embodiment 2 has used benzene and water.Although total DIB, selectivity and the transformation efficiency of described Comparative Examples and embodiment are much at one, the productivity of the p-DIB among the described embodiment is far above Comparative Examples.Particularly, high 3 times in the productivity ratio Comparative Examples 1 of the p-DIB among the embodiment 1 or 2.This may be to be caused by the control to the iodination reaction actuator temperature.For improving the productivity of p-DIB, should increase the input rate of feed reactants.Yet, shown in the reaction result of Comparative Examples 2, have only at reactant under the situation of benzene and iodine, when increasing the feed rate of reactant, the temperature on the top of iodination reaction device can raise uncontrollablely.According to the temperature curve in the Comparative Examples 1, the upper temp of described iodination reaction device is higher 40 ℃ than core temperature.In addition, consider CO
2With the amount of carbon deposits, embodiment 1 and 2 is better than Comparative Examples 1 and 2.This is to be caused by the temperature control to the iodination reaction device.
Therefore, comprise a kind of aromatics, a kind of di-iodo aromatic compound or water and iodine (I by making with zeolite catalyst and oxygen
2) the reactant iodate, preparation method of the present invention helps controlling the temperature of iodination reaction device, thus improve the per unit weight catalyzer iodinated aromatic compounds productivity and improve the especially production of p-DIB of DIB.Therefore, preparation method of the present invention can extensively be used for the production of described iodinated aromatic compounds effectively.
Claims (10)
1. method for preparing iodinated aromatic compounds comprises:
In the presence of zeolite catalyst and oxygen, make and comprise a kind of aromatics, a kind of di-iodo aromatic compound or water and iodine (I
2) the mixture iodate.
2. the process of claim 1 wherein that described aromatics is selected from benzene, naphthalene and biphenyl.
3. the process of claim 1 wherein that described di-iodo aromatic compound is selected from benzene diiodide, two iodate naphthalenes and two iodate biphenyl.
4. the process of claim 1 wherein that described di-iodo aromatic compound is with respect to the mol ratio use of described aromatics with 2-10mol%.
5. the process of claim 1 wherein that water uses with the mol ratio of 5-30mol% for described aromatics.
6. the process of claim 1 wherein that described zeolite catalyst is selected from Na-13X zeolite, y-type zeolite, ZSM5 zeolite and K-13X zeolite.
7. the method for claim 6, wherein said zeolite catalyst is the Na-13X zeolite.
8. the process of claim 1 wherein that described iodination reaction carries out under 230-350 ℃ and normal pressure to 5 normal atmosphere.
9. the method for claim 1 also comprises:
Make the di-iodo aromatic compound circulation that comprises di-iodo aromatic compound, adjacent di-iodo aromatic compound and a di-iodo aromatic compound,
Wherein said di-iodo aromatic compound obtains in the following way:
Distillation is by comprising described aromatics, described di-iodo aromatic compound or water and iodine (I
2) the iodate product that obtains of mixture, and overhead product carried out crystallization and solid-liquid separation.
10. the method for claim 9 also comprises:
Will be by comprising described aromatics, described di-iodo aromatic compound or water and iodine (I
2) the iodate product that obtains of mixture be delivered to first distillation tower (C10) from iodination reaction device (R01), described aromatics of Separation and Recovery and water from the iodate product at first distillation tower (C10) top then;
The overhead product of first distillation tower (C10) bottom is delivered to second column (C20), then single iodinated aromatic compounds of Separation and Recovery and iodine from the overhead product at second column (C20) top;
The overhead product of second column (C20) bottom is delivered to the 3rd distillation tower (C30), Separation and Recovery comprises and then they is delivered to di-iodo aromatic compound to di-iodo aromatic compound, adjacent di-iodo aromatic compound and a di-iodo aromatic compound in crystallization and the solid-liquid separator (D10) from the overhead product at the 3rd distillation tower (C30) top then;
The Separation and Recovery solid phase is to di-iodo aromatic compound with comprise the mother liquor of liquid phase to di-iodo aromatic compound, adjacent di-iodo aromatic compound and a di-iodo aromatic compound from crystallization and solid-liquid separator (D10); With
By making described di-iodo aromatic compound circulation in the part input iodination reaction device (R01) with described mother liquor.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2007-0132303 | 2007-12-17 | ||
| KR1020070132303 | 2007-12-17 | ||
| KR1020070132303A KR101123148B1 (en) | 2007-12-17 | 2007-12-17 | Method of preparing iodinated aromatic compounds |
| PCT/KR2008/007483 WO2009078667A2 (en) | 2007-12-17 | 2008-12-17 | Method of preparing iodinated aromatic compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101679152A true CN101679152A (en) | 2010-03-24 |
| CN101679152B CN101679152B (en) | 2014-08-06 |
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|---|---|---|---|
| CN200880016638.7A Expired - Fee Related CN101679152B (en) | 2007-12-17 | 2008-12-17 | Method of preparing iodinated aromatic compounds |
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|---|---|
| US (1) | US8309775B2 (en) |
| EP (1) | EP2222621B1 (en) |
| JP (2) | JP5902885B2 (en) |
| KR (1) | KR101123148B1 (en) |
| CN (1) | CN101679152B (en) |
| ES (1) | ES2427734T3 (en) |
| HK (1) | HK1142590A1 (en) |
| WO (1) | WO2009078667A2 (en) |
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| US8674148B2 (en) * | 2007-10-23 | 2014-03-18 | Sk Chemicals Co., Ltd. | Manufacturing process for iodinated aromatic compounds |
| KR101004369B1 (en) * | 2008-12-11 | 2010-12-27 | 에스케이케미칼주식회사 | Process for producing aromatic iodide compound |
| KR101673048B1 (en) * | 2013-09-03 | 2016-11-04 | 주식회사 엘지화학 | Method for preparing polyphenyl sulfide resin |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1176856B (en) * | 1984-10-05 | 1987-08-18 | Montedipe Spa | METHOD FOR THE SYNTHESIS OF IODOBENZENE |
| IT1176981B (en) * | 1984-10-16 | 1987-08-26 | Montedipe Spa | METHOD FOR THE SYNTHESIS OF IODOBENZENE |
| IT1197862B (en) * | 1986-08-11 | 1988-12-21 | Montedipe Spa | PROCESS FOR THE CATALYTIC TRANS-HALOGENATION OF A POLY-IODE BENZENE |
| US4778938A (en) * | 1986-09-29 | 1988-10-18 | Eastman Kodak Company | Processes for preparing iodinated aromatic compounds |
| US4746758A (en) | 1986-09-29 | 1988-05-24 | Eastman Kodak Company | Processes for preparing iodinated aromatic compounds |
| US4792642A (en) * | 1987-03-25 | 1988-12-20 | Eastman Kodak Company | Process for preparing iodinated aromatic compounds |
| US4792641A (en) * | 1987-03-25 | 1988-12-20 | Eastman Kodak Company | Process for preparing iodinated aromatic compounds |
| US4778940A (en) * | 1987-03-25 | 1988-10-18 | Eastman Kodak Company | Process for preparing iodinated substituted aromatic compounds |
| US4810826A (en) * | 1988-03-17 | 1989-03-07 | Eastman Kodak Company | Liquid-phase process for the oxyiodination of naphthalene |
| US5082982A (en) * | 1990-11-02 | 1992-01-21 | Eastman Kodak Company | Oxyiodination process for manufacture of 2,6-diiodonaphthalene |
| KR101112173B1 (en) * | 2006-12-29 | 2012-02-24 | 에스케이케미칼주식회사 | Method of preparing mono-iodo benzene through transiodination |
| WO2009054555A1 (en) * | 2007-10-23 | 2009-04-30 | Sk Chemicals Co., Ltd. | Manufacturing process for iodinated aromatic compounds |
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- 2008-12-17 JP JP2010537874A patent/JP5902885B2/en active Active
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| Publication number | Publication date |
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| EP2222621A4 (en) | 2012-02-22 |
| CN101679152B (en) | 2014-08-06 |
| WO2009078667A2 (en) | 2009-06-25 |
| JP2011506431A (en) | 2011-03-03 |
| HK1142590A1 (en) | 2010-12-10 |
| US20100222617A1 (en) | 2010-09-02 |
| EP2222621B1 (en) | 2013-07-17 |
| EP2222621A2 (en) | 2010-09-01 |
| JP5902885B2 (en) | 2016-04-13 |
| US8309775B2 (en) | 2012-11-13 |
| ES2427734T3 (en) | 2013-10-31 |
| JP2014210779A (en) | 2014-11-13 |
| KR101123148B1 (en) | 2012-03-19 |
| KR20090064922A (en) | 2009-06-22 |
| WO2009078667A3 (en) | 2009-09-17 |
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